Astringent compositions

ABSTRACT

THE PRESENT INVENTION IS CONCERNED WITH AEROSOL SPRAY ANTI-PERSPIRANT COMPOSITIONS OF THE TYPE IN WHICH THE ASTRINGENT MATERIAL IS SUSPENDED AS A SOLID IN AN ANHYDROUS LIQUID VEHICLE AND DISPENSED IN THIS FORM AND MORE PARTICULARLY WITH ANTI-PERSPIRANT COMPOSITIONS OF THIS TYPE WHICH HAVE SUBSTANTIALLY REDUCED PROPENSITY TO STAIN CLOTHING. GENERALLY SUCH IMPROVEMENTS ARE BROUGHT ABOUT BY USING AS THE LIQUID VEHICLE FOR SUCH COMPOSITIONS ESTERS OF MONO-, DI-BASIC ACIDS WHICH ARE MISCIBLE WITH THE PROPELLANT AND WHICH ARE SELECTED FROM THE GROUP CONSISTING OF METHYL LACTATE, ESTER LACTATE, PROPYL LACTATE, ISOPROPYL LACTATE, BUTYL LACTATE DIMETHYL SUCCINATE, DIETHYL SUCCINATE, DIISOPROPYL SUCCINATE, DIPROPYL SUCCINATE, DIBUTYL SUCCINATE, DIETHYL MALATE, DIETHYL MALEATE, DIETHYL TARTRATE, DIISOPROPYL TARTRATE, DIPROPYL TARTRATE, DIBUTLY TARTRATE, DIMETHYL GLUTARATE, DIETHYL GLUTARATE, DIISOPROPYL GLUTARATE, DIPROPYL GLUTARATE, DIBUTYL GLUTARATE, DIMETHYL ADIPATE AND DIETHYL ADIPATE.

United States Patent 3,833,720 ASTRINGENT COMPOSITIONS James M. Crotty, Beverly, Daniel C. Geary, Acton, Ed-

ward F. Levy, Newtonville, Dolores V. Lopiekes, Bridgewater, Robert L. Raymond, Marblehead, and Bernard Siegal, Bedford, Mass., assignors to The Gillette Company, Boston, Mass. No Drawing. Filed July 14, 1972, Ser. No. 272,043 Int. Cl. A61k 7/00 U.S. Cl. 424-47 6 Claims ABSTRACT OF THE DISCLOSURE The present invention is concerned with aerosol spray anti-perspirant compositions of the type in which the astringent material is suspended as a solid in an anhydrous liquid vehicle and dispensed in this form and more particularly with anti-perspirant compositions of this type which have substantially reduced propensity to stain clothing. Generally such improvements are brought about by using as the liquid vehicle for such compositions esters of mono-, di-basic acids which are miscible with the propellant and which are selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, dimethyl succinate, diethyl succinate, diisopropyl succinate, dipropyl succinate, dibutyl succinate, diethyl malate, diethyl maleate, diethyl tartrate, diisopropyl tartrate, dipropyl tartrate, dibutyl tartrate, dimethyl glutarate, diethyl glutarate, diisopropyl glutarate, dipropyl glutarate, dibutyl glutarate, dimethyl adipate and diethyl adipate.

Aerosol anti-perspirant compositions in which the astringent material, e.g., aluminum chlorohydroxide, is dispensed as a solid suspended in an anhydrous hydrophobic liquid vehicle such as mineral oil, isopropyl myristate or isopropyl palmitate have been widely marketed. Although such compositions are elfective in reducing perspiration they have a tendency to impart stains to clothing which (stains) remain subsequent to laundering. The present invention is concerned with providing anti-perspirant compositions of this type which have substantially reduced tendency to stain clothing.

It has been found in the present invention that the staining due to such compositions can be substantially reduced by using as the liquid vehicle for said compositions an ester which is miscible with the propellant and which is selected from the group consisting of: methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, dimethyl succinate, diethyl succinate, diisopropyl succinate, dipropyl succinate, dibutylsuccinate, diethyl malate, diethyl maleate, diethyl tartrate, diisopropyl tartrate, dipropyl tartrate, dibutyl tartrate, dimethyl glutarate, diethyl glutarate, diisopropyl glutarate, dipropyl glutarate, dibutyl glutarate, dimethyl adipate and diethyl adipate.

Generally the astringent may be selected from any of the materials of this nature which are available, e.g. aluminum sulfate, aluminum chloride, aluminum chlorhydroxides such as A1(OH) Cl and Al (OH) Cl aluminum sulfocarbolate, zinc chloride, Zinc sulfocarbolate, zinc sulfate, zirconium oxychloride, sodium zirconium lactate, sodium zirconium glycolate, zirconyl hydroxy chloride, zirconium sulfate, physical mixtures of the above, and mixed compounds and complexes comprising 2 or more of the above cations such as a mixed aluminum zirconium chlorhydroxide complex. The preferred astringents for use in the composition of this invention are the aluminum chlorhydroxides. The amount of astringent employed may be varied but in most compositions it will be present in amounts ranging between about 0.5% to about 3,333,720 Patented Sept. 3, 1974 10% by weight of the total composition including the propellant. In preferred compositions, it will be present in amounts ranging between about 1 to about 7.5%. Further the astringent should be finely ground in order to prevent the valve from clogging. Usually it the particle size is less than 100 microns and preferably less than 60 microns, clogging will be held to a minimum.

The ester is present in amounts such that in combination with the propellant it will be the continuous phase of the dispersion or suspension. As can be appreciated, this amount will vary depending upon the amount of astringent employed. In most instances, the ester will comprise from about 0.5 to about 50% by weight of the total composition including the propellant. In preferred compositions, the ester is present in amounts ranging between about 0.5 to about 15%.

Generally any of the materials which have been employed as propellants in aerosol compositions may be used in the compositions of the present invention; provided of course that they are miscible with the liquid vehicle. As examples of such materials mention may be made of: dichlorodifluoromethane, trichloromonofluoromethane, trichlorotrifiuoroethane, tetrafluorodichloroethane, butane, propane, isobutane and mixtures and blends of the above. The propellant will generally be present in amounts which will be sufficient to dispense all of the composition at a moderate velocity. In most instances the compositions will have vapor pressures ranging between 15 and p.s.i.g. and preferably between 20 and 40. Generally the propellant will be present in amounts varying between 50 to 98% by weight of the total composition and preferably between 70 to 98%.

The preferred compositions of the present invention will further include a suspending, dispersing of flocculating agent to prevent the astringent from agglomerating or settling. As examples of such agents, mention may be made of clays, such as bentonite, modified clays, e.g. the reaction product of bentonite and a surface active quaternary salt, silicas such as colloidal silicon dioxide, silicates, polymeric suspending agents such as cellulose and derivatives thereof and surfactants such as high molecular weight amides, e.g. lauryl monoethanolamide. If desired, the compositions may further include other ingredients such as perfumes, emollients, talc, starches, antibacterials, etc.

The effectiveness of the compositions of the present invention in reducing stain was demonstrated by using the esters disclosed herein on a weight basis in place of isopropyl palrnitate in a standard formula and measuring the extent of staining it caused as compared with the composition containing isopropyl palmitate. The standard formula was as follows:

Percent by weight Vehicle 6.12 Hexachlorophene 0.04 Aluminum Chlorhydroxide 3.40 Pyrogenic Colloidal Silica 0.35 Perfume 0.35 Propellant mixture:

70% by weight trichlorofluoromethane 89 74 30% by weight dichlorodifluoromethane unlaundered material using a Photovolt Model 670 Reflectometer equipped with a 610-T search unit and a green filter. The average of 12 readings was designated as R0.

(3) The swatches were laundered in an apartment size washer for 15 minutes in 10 liters of hot (about 55 C.) tap water containing 30 g. of an alkyl aryl sulfonate detergent and 100 ml. of a commercial hypochlorite bleach. The swatches were rinsed for two 10 minute cycles in hot tap water and then for a 10 minute cycle in cool distilled water. The swatches were dried for 24 hours at 60 C. in a 220 Volt Freas Model 625 forced draft oven.

(4) Five swatdhes of the fabric were mounted on poster boards and the center portions of each were subjected to three two-second sprays of the formulation which was being tested. An average of about six grams of the formu lation was dispensed over the six-second period. The swatches were allowed to stand for '30 minutes and then smeared with a spatula to an even out irregularities in the application area.

(5) The swatches were laundered and dried in the same manner as set forth in step 3 above.

(6) The Photovolt Reflectometer was warmed up for 30 minutes and three readings were made of the stained area. The cloth was rotated 90 and three additional readings were made. The average of the six readings in the stained area was referred to as R (7) Three reflectance readings were taken in the edge or non-stained areas and the cloth was rotated 90 and three additional readings were taken. The average of the six readings in the non-stain area were were referred to as RE.

(8) The Stain Index was calculated for each formulation after each cycle by using the following equation:

Stain Index= 100 RO RS where R =average of six reflectance readings in edge or nonstain region.

Rg=average of six reflectance readings in stain areas.

R =reflectance of unused, unwashed, virgin material.

The propensity of the formulation to stain clothing was indicated by an increase in the stain index as the above cycle comprising steps 4 through 7 was continually repeated.

Table I summarizes the results of tests wherein esters within the scope of the present invention were run against isopropyl palmitate.

TABLE I.STAIN INDIOES TEST MATERIALS VS. ISO- PROPYL PALMITATE (IPP) Stain cycle Test N 0. Materials 4 5 6 Average 1 Diethyl suceinate 17. 2 15. 5 15. 2 16. IPP 49. 6 53. 4. 54. a 52.

2-.---. Dibutyl tartrate- 13. 2 0 2. 8 5. 3 P 55. 9 58. 8 55. 8 56. 8

3- Ethyl lactate.-----.-;- 0 0 e 0 g 72. 5 54. 5 55. 5 60. 8 Dihutyl suecinate.-- 0 0 0 0 Dibutyl glutarate--- 0 0 0 o Butyl lactate 0 0 0 0 Dimethyl succinate- 0 0 0 0 Dimethyl adipate-.. 10 O O 3. 3 Dimethyl glutamate 17 O 0 5. 7 42. 5 47. 6 50. 8 47. g

5 Diethyl maleate 20. 6 16.7 20 19. 1 Diethyl malate--- 28. 0 29. 2 28. 8 25. 7 Diethyl adipate 11. 2 0 5. 5 5. 6 64. 2 60. 5 56. 8 60. 5

6 Methyl lactate 12 22. 6 21 18. 5 70. 2 76. 5 69 71. 9

.... Diethyl tartrate-.- 30. 6 29. 5 30. 1 l? 51. 4 52. 1 51. 8

8 Dlisopropyl succinate- 0 0 0 0 IPP 64. 5 57. 5 64. 5 62. 2

Not. run.-

As can be noted from the above, the esters within the scope of the present invention have substantially lower stain indices than the isopropyl palmitate.

Having thus described the invention what is claimed is:

1. An aerosol composition having improved anti-stain properties, said composition comprising 0.5% to 10% by weight of an astringent material selected from the group consisting of aluminum sulfate, aluminum chloride, aluminum chlorhydroxide, aluminum sulfocarbolate, zinc chloride, zinc sulfocarbolate, zinc sulfate, zirconium oxychloride, sodium zirconium lactate, sodum zirconium glycolate, zirconyl hydroxy chloride, zirconium sulfate and aluminum zirconium chlorhydroxide complex, 50 to 98% by weight of a propellant selected from the group consisting of dichlorodifluoromethane, trichloromonofiuoromethane, trichlorotrifluoroethane, tetrafluorodichloroethane, butane, propane, isobutane and mixtures and blends thereof and 0:5 to 50% by Weight of a vehicle, said astringent material being insoluble in both said propellant and said vehicle and said vehicle being miscible with the propellant and being selected from the group consisting of: methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, dimethyl succinate, diethyl succinate, diisopropyl succinate, dipropyl succinate, dibutyl succinate, diethyl malate, diethyl maleate, diethyl tartrate, diisopropyl tartrate, dipropyl tartrate, dibutyl tartrate, dimethyl glutarate, diethyl glutarate, diisopropyl glutarate, dipropyl glutarate, dibutyl glutarate, dimethyl adipate and diethyl adipate said percentages are based on Weight of the total composition.

2. A composition as defined in claim 1 wherein said astringent material is aluminum chlorhydroxide.

3. A composition as defined in claim 1 wherein said vehicle is dibutyl succinate.

4. A composition as defined in claim 3 wherein the astringent material is aluminum chlorhydroxide.

5. A composition as defined in claim 1 wherein said vehicle is dibutyl glutarate.

6. A composition as defined in claim 1 wherein said vehicle is butyl lactate.

References Cited UNITED STATES PATENTS 3,030,274 4/1962 Grant 42468 X 3,544,258 12/1970 Presant ct a1. 42447 X FOREIGN PATENTS 687,228 1/1967 Belgium 424-47 987,301 3/1965 Great Britain 4M-47 OTHER REFERENCES De Navarre International Encyclopedia of Cosmetic Material Trade Names, 1957, pp. 11, 40, 122 ,199, 2.28, 323.

ALBERT T. MEYERS, Primary Examiner D. R. ORE, Assistant Examiner 

